U.S. patent application number 09/682737 was filed with the patent office on 2003-04-24 for terbium- or lutetium - containing garnet phosphors and scintillators for detection of high-energy radiation.
Invention is credited to Comanzo, Holly Ann, Setlur, Anant Achyut, Shiang, Joseph John, Srivastava, Alok Mani.
Application Number | 20030075706 09/682737 |
Document ID | / |
Family ID | 24740928 |
Filed Date | 2003-04-24 |
United States Patent
Application |
20030075706 |
Kind Code |
A1 |
Shiang, Joseph John ; et
al. |
April 24, 2003 |
Terbium- or lutetium - containing garnet phosphors and
scintillators for detection of high-energy radiation
Abstract
Scintillator compositions having a garnet crystal structure
useful for the detection of high-energy radiation, such as X,
.beta., and .gamma. radiation, contain (1) at least one of terbium
and lutetium; (2) at least one rare earth metal; and (3) at least
one of Al, Ga, and In. Terbium or lutetium may be partially
substituted with Y, La, Gd, and Yb. In particular, the scintillator
composition contains both terbium and lutetium. The scintillators
are characterized by high light output, reduced afterglow, short
decay time, and high X-ray stopping power.
Inventors: |
Shiang, Joseph John;
(Niskayuna, NY) ; Setlur, Anant Achyut;
(Niskayuna, NY) ; Srivastava, Alok Mani;
(Niskayuna, NY) ; Comanzo, Holly Ann; (Niskayuna,
NY) |
Correspondence
Address: |
GENERAL ELECTRIC COMPANY
GLOBAL RESEARCH CENTER
PATENT DOCKET RM. 4A59
PO BOX 8, BLDG. K-1 ROSS
NISKAYUNA
NY
12309
US
|
Family ID: |
24740928 |
Appl. No.: |
09/682737 |
Filed: |
October 11, 2001 |
Current U.S.
Class: |
252/301.4R ;
250/361R; 378/19 |
Current CPC
Class: |
C04B 2235/443 20130101;
C04B 2235/6587 20130101; C04B 2235/652 20130101; C04B 2235/449
20130101; C04B 2235/3217 20130101; C04B 2235/764 20130101; C04B
35/62615 20130101; C04B 2235/3224 20130101; G01T 1/2023 20130101;
C04B 2235/3229 20130101; C04B 35/6265 20130101; C04B 2235/44
20130101; C04B 2235/445 20130101; C04B 35/44 20130101; C04B
2235/6582 20130101; C04B 2235/658 20130101 |
Class at
Publication: |
252/301.40R ;
378/19; 250/361.00R |
International
Class: |
G01T 001/20 |
Claims
1. A scintillator composition comprising a garnet that comprises at
least one metal selected from the group consisting of terbium and
lutetium; said garnet being activated with at least one rare-earth
metal selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Dy,
Ho, Er, and Tm; said scintillator being capable of emitting visible
light in response to high-energy radiation selected from the group
consisting of X, .beta., and .gamma. radiation.
2. The scintillator composition according to claim 1 having a
formula of (Tb.sub.1-yCe.sub.y).sub.aD.sub.zO.sub.12; wherein D is
at least one metal selected from the group consisting of Al, Ga,
and In; a is in a range from about 2.8 to and including 3; y is in
a range from about 0.0005 to about 0.2; and z is in a range from
about 4 to and including 5.
3. The scintillator composition according to claim 1 having a
formula of (Lu.sub.1-yCe.sub.y).sub.aD.sub.zO.sub.12; wherein D is
at least one metal selected from the group consisting of Al, Ga,
and In; a is in a range from about 2.8 to and including 3; y is in
a range from about 0.0005 to about 0.2; and z is in a range from
about 4 to and including 5.
4. The scintillator composition according to claim 1 having a
formula of (G.sub.1-x-yA.sub.xRE.sub.y).sub.aD.sub.zO.sub.12
wherein G is at least one metal selected from the group consisting
of Tb and Lu; A is at least one rare earth metal selected from the
group consisting of Y, La, Gd, Lu, and Yb when G is Tb and selected
from the group consisting of Y, La, Gd, Tb, and Yb when G is Lu; RE
is at least one rare earth metal selected from the group consisting
of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, and Tm; D is at least one metal
selected from the group consisting of Al, Ga, and In; a is a range
from about 2.8 to and including 3; x is in a range from 0 to about
0.5; y is in a range from about 0.0005 to about 0.2; and z is in a
range from about 4 to and including 5.
5. The scintillator composition according to claim 4, wherein a is
preferably in a range from about 2.9 to and including 3.
6. The scintillator composition according to claim 4, wherein x is
preferably in a range from 0 to about 0.3 and more preferably from
0 to about 0.2.
7. The scintillator composition according to claim 4, wherein y is
preferably in a range from about 0.005 to about 0.1 and more
preferably from about 0.005 to about 0.07.
8. The scintillator composition according to claim 4, wherein z is
preferably in a range from about 4.5 to and including 5 and more
preferably from about 4.6 to and including 5.
9. The scintillator composition according to claim 4, wherein the
scintillator composition comprises praseodymium oxide in an amount
from about 2 to about 500 mole parts per million ("ppm").
10. The scintillator composition according to claim 4, wherein A is
Lu, RE is Ce, and D is Al.
11. The scintillator composition according to claim 1, wherein said
scintillator composition has a formula of
(Tb.sub.1-yCe.sub.y).sub.3(Al.s-
ub.1-r-sGa.sub.rIn.sub.s).sub.zO.sub.12 where y is in a range from
about 0.0005 to about 0.2, z is in a range from about 4 to about 5,
0.ltoreq.r.ltoreq.0.5, 0<s.ltoreq.0.5, and r+s<1.
12. The scintillator composition according to claim 1, wherein said
scintillator composition has a formula of
(Tb.sub.1-yCe.sub.y).sub.3(Al.s-
ub.1-r-sGa.sub.rIn.sub.s).sub.zO.sub.12 where y is in a range from
about 0.0005 to about 0.2, z is in a range from about 4 to about 5,
0.ltoreq.r.ltoreq.0.5, 0<s.ltoreq.0.5, and r+s<1.
13. The scintillator composition according to claim 14, wherein y
is preferably in a range from about 0.005 to about 0.1 and more
preferably from 0.005 to 0.07; z is preferably in a range from
about 4.5 to about 5 and more preferably from about 4.6 to about 5;
r is preferably in a range from about 0.005 to about 0.3 and more
preferably from about 0.05 to about 0.2; and s is preferably in a
range from about 0.005 to about 0.3 and more preferably from about
0.05 to about 0.2.
14. The scintillator composition according to claim 15, wherein y
is preferably in a range from about 0.005 to about 0.1 and more
preferably from 0.005 to 0.07; z is preferably in a range from
about 4.5 to about 5 and more preferably from about 4.6 to about 5;
r is preferably in a range from about 0.005 to about 0.3 and more
preferably from about 0.05 to about 0.2; and s is preferably in a
range from about 0.005 to about 0.3 and more preferably from about
0.05 to about 0.2.
15. The scintillator composition according to claim 1 having a
formula of
(Tb.sub.1-y-u-v-wCe.sub.yY.sub.uGd.sub.vSm.sub.w).sub.3Al.sub.zO.sub.12
where y is in a range from about 0.0005 to about 0.2, z is in a
range from about 4 to about 5, 0.ltoreq.u, v, w.ltoreq.0.5, and
0.0005.ltoreq.y+u+v+w<1.
16. The scintillator composition according to claim 1 having a
formula of
(Tb.sub.1-y-u-v-wCe.sub.yY.sub.uGd.sub.vSm.sub.w).sub.3Al.sub.zO.sub.12
where y is preferably in a range from about 0.005 to about 0.1 and
more preferably from about 0.005 to about 0.07; z is preferably in
a range from about 4.5 to about 5 and more preferably from about
4.6 to about 5; each of u, v, and w is preferably in a range from
about 0.005 to about 0.3 and more preferably from about 0.005 to
about 0.1.
17. A method for producing a garnet scintillator composition, said
method comprising the steps of: (1) providing amounts of: (a)
oxygen-containing compounds of at least one first metal selected
from the group consisting of terbium and lutetium; (b)
oxygen-containing compounds of at least one rare-earth metal
selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Dy, Ho,
Er, and Tm; and (c) oxygen-containing compounds of at least one
second metal selected from the group consisting of Al, Ga, and In;
(2) mixing together said oxygen-containing compounds to form a
mixture; and (3) firing said mixture in a reducing atmosphere at a
temperature for a time sufficient to convert said mixture to a rare
earth-activated garnet scintillator composition; wherein said
amounts of oxygen-containing compounds are chosen to obtain the
final desired composition of said garnet scintillator, and said
garnet scintillator is capable of emitting visible light in
response to an excitation of high-energy radiation selected from
the group consisting of X, .beta., and .gamma. radiation.
18. The method according to claim 17 further comprising the step of
mixing at least one compound selected from the group consisting of
halides and carbonates of at least one metal selected from the
group consisting of Tb, Lu, Al, Ga, In, Y, La, Ce, Pr, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, Yb, Na, K, Rb, and Cs in said mixture in a
quantity sufficient to act as a flux during said firing.
19. The method according to claim 18, wherein said quantity of said
compound is less than about 20 percent by weight of a total weight
of said mixture.
20. The method according to claim 17, wherein said temperature is
in a range from about 900.degree. C. to about 1600.degree. C.
21. The method according to claim 20, wherein said temperature is
preferably from about 1000.degree. C. to about 1500.degree. C.
22. The method according to claim 18, wherein said reducing
atmosphere comprises a gas selected from the group consisting of
hydrogen, carbon monoxide, and mixtures thereof and an inert gas
selected from the group consisting of nitrogen, helium, neon,
argon, krypton, and xenon.
23. A method for producing a garnet scintillator composition, said
method comprising the steps of: (1) preparing a first solution from
amounts of: (a) compounds of at least one first metal selected from
the group consisting of Tb and Lu; (b) compounds of at least one
rare-earth metal selected from the group consisting of Y, La, Ce,
Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb; and (c) at least one
compound of at least one second metal selected from the group
consisting of Al, Ga, and In; (2) providing a second solution
selected from the group consisting of ammonium hydroxide,
hydroxides of at least one of Tb, Lu, Y, La, Ce, Pr, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, Yb, Al, Ga, and In; alkyl esters of a
dicarboxylic acid selected from the group consisting of oxalic
acid, malonic acid, succinic acid, and glutaric acid; amines
selected from the group consisting of methanolamine, ethanolamine,
propanolamine, dimethanolamine, diethanolamine, dipropanolamine,
trimethanolamine, triethanolamine, and tripropanolamine; and
mixtures thereof; (3) mixing together said first solution and said
second solution to form a precipitate mixture of oxygen-containing
compounds of at least one first metal, at least one rare-earth
metal, and at least one second metal; (4) separating said
precipitate mixture from a supernatant liquid; (5) drying said
separated precipitate mixture; and (6) firing said dried
precipitate mixture at a temperature and for a time sufficient to
convert said dried precipitate mixture to a garnet scintillator
composition; wherein said amounts of compounds are chosen to obtain
a final desired composition of said garnet scintillator, and said
garnet scintillator is capable of emitting visible light in
response to an excitation of high-energy radiation selected from
the group consisting of X, .beta., and .gamma. radiation.
24. The method according to claim 23 further comprising the step of
adding at least one compound selected from the group consisting of
halides and carbonates of at least one metal selected from the
group consisting of Tb, Lu, Al, Ga, In, Y, La, Ce, Pr, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, Yb, Na, K, Rb, and Cs in said first solution in
a quantity sufficient to act as a flux during said firing.
25. The method according to claim 24, wherein said quantity of said
compound is less than bout 20 percent by weight of a total weight
of said dried precipitate.
26. The method according to claim 23 further comprising the step of
calcining said dried precipitate mixture in atmosphere containing
oxygen at a temperature in a range from about 400.degree. C. to
about 900.degree. C. before the firing step.
27. The method according to claim 23, wherein said firing is
conducted at a temperature in a range from about 900.degree. C. to
about 1600.degree. C.
28. The method according to claim 27, wherein said temperature is
preferably in a range from about 1000.degree. C. to about
1500.degree. C.
29. A detector element of an X-ray CT scanner comprising a garnet
scintillator composition of claim 1.
30. A detector element of an X-ray CT scanner comprising a garnet
scintillator composition of claim 2.
31. A detector element of an X-ray CT scanner comprising a garnet
scintillator composition of claim 3.
32. A detector element of an X-ray CT scanner comprising a garnet
scintillator composition of claim 4.
33. A detector element of an X-ray CT scanner comprising a garnet
scintillator composition of claim 10.
Description
BACKGROUND OF INVENTION
[0001] The present invention relates to terbium- or
lutetium-containing phosphors and scintillators having a garnet
structure activated with rare-earth metal ions useful for the
detection of high-energy radiation. In particular, the present
invention relates to a terbium or lutetium aluminum oxide garnet
X-ray phosphor or scintillator activated with cerium. The present
invention also relates to X-ray detectors and detection systems
incorporating an X-ray phosphor or scintillator comprising a
terbium- or lutetium-containing garnet activated with rare-earth
metal ions.
[0002] The terms "phosphor" and "scintillator" are used herein in
an interchangeable way to mean a solid-state luminescent material
that emits visible light in response to stimulation by high-energy
radiation such as X, .beta., or .gamma. radiation. The term
"high-energy radiation" means electromagnetic radiation having
energy higher than that of ultraviolet radiation. Solid-state
scintillator materials are in common use as component of radiation
detectors in apparatuses such as counters, image intensifiers, and
computed tomography ("CT") scanners. Scintillator materials
especially find widespread use in X-ray detectors. One embodiment
of the present generation of solid-state ceramic scintillators
comprises oxide mixtures in which a rare-earth oxide is present as
an activator, along with various combined matrix elements, which
are also usually rare-earth oxides. Other metallic compounds may
also be present as additives for specific purposes. These
scintillators have been characterized by the advantageous
properties of high efficiency, moderate decay time, low afterglow
and little or no radiation damage upon exposure to high X-ray
doses.
[0003] One important property of CT systems is scan time which is
the time required for a CT system to scan and acquire an image of a
slice of the object under observation. Scan times of CT systems are
related to primary decay time (sometimes simply "decay
time"hereinafter) of the scintillator roughly by a factor of 1000.
Thus, a scintillator having a decay time of 1 millisecond will
typically produce a scan time of about 1 second. The scanning units
containing the present generation of scintillators have scan times
on the order of 1 second, and in any event no lower than about 0.7
second.
[0004] In future generations of CT scanners and the like, shorter
scan times are desired. This is true because decreasing scan time
makes possible an increase in patient volume covered in a given
time or an increase in the number of scans within a single breath
hold. Also, it reduces image blurring due to motion of internal
organs and of non-cooperating patients, including pediatric
patients.
[0005] Shorter scan times are achievable if the primary decay time
of the phosphor or scintillator is shortened. In general, scan time
in seconds is associated with a primary decay time of an equal
number of milliseconds. As the speed of data processing in CT
scanners increases due to advances in electronic circuit designs,
it is desired to have faster scintillators, i.e., shorter time
between receipts of stimulating radiation pulses so to fully take
advantage of the capability of the scanner. Therefore, any
measurable percentage decrease in decay time from that exhibited by
the present generation of ceramic scintillators would be a distinct
improvement, particularly when accompanied by the other
advantageous properties described above.
[0006] Among the preferred scintillator compositions in the present
generation of CT scanners are the ceramic scintillators employing
at least one of the oxides of lutetium, yttrium, and gadolinium as
matrix materials. These are described in detail, for example, in
U.S. Pat. Nos. 4,421,671; 4,473,513; 4,525,628; and 4,783,596. They
typically comprise a major proportion of yttria (Y.sub.2O.sub.3),
up to about 50 mole percent gadolinia (Gd.sub.2O.sub.3) and a minor
activating proportion (typically about 0.02-12, preferably about
1-6 and most preferably about 3 mole percent) of a rare earth
activator oxide. Suitable activator oxides, as described in the
aforementioned patents, include the oxides of europium, neodymium,
ytterbium, dysprosium, terbium, and praseodymium.
Europium-activated scintillators are often preferred in commercial
X-ray detectors by reason of their high luminescent efficiency, low
afterglow level, and other favorable characteristics. Europium is
typically present therein in amounts up to 30 and most often up to
about 12, preferably in the range of 1-6 and most preferably about
3 mole percent. Decay times of such scintillators are on the order
of 0.9-1.0 millisecond. However, such decay times still leave much
to be desired.
[0007] The search thus continues for ceramic scintillator
compositions having shorter decay times in combination with the
aforementioned other advantageous properties.
SUMMARY OF INVENTION
[0008] The present invention provides improved scintillator
compositions comprising a terbium- or lutetium-containing garnet
activated with at least one rare-earth metal. The scintillator
compositions are useful in the detection of high-energy radiation,
such as X, .beta., or .gamma. radiation. Particularly, the
scintillators of the present invention have higher light output,
reduced afterglow, short decay time, and high X-ray stopping power
in X-ray detection applications.
[0009] According to one aspect of the present invention, the
scintillator compositions comprise terbium-containing garnet
activated with at least one rare-earth metal having a general
formula of (G.sub.1-x-yA.sub.xRE.su- b.y).sub.aD.sub.zO.sub.12,
wherein G is at least one metal selected from the group consisting
of Tb and Lu; A is a member selected from the group consisting of
Y, La, Gd, Lu, and Yb when G is Tb, and selected from the group
consisting of Y, La, Gd, Tb, and Yb when G is Lu; RE is at least
one member selected from the group consisting of Ce, Pr, Nd, Sm,
Eu, Dy, Ho, Er, and Tm; D is at least one member selected from the
group consisting of Al, Ga, and In; a is in the range from about
2.8 to and including 3; x is in the range from 0 to about 0.5; y is
in the range from about 0.0005 to about 0.2; and z is in the range
from about 4 to and including 5. In one aspect of the present
invention 4<z<5.
[0010] According to another aspect of the present invention, a
method for producing a rare earth-activated garnet scintillator
containing Tb or Lu useful for a detection of X, .beta., or .gamma.
radiation comprises the steps of: (1) providing amounts of
oxygen-containing compounds of at least one first metal selected
from the group consisting of terbium and lutetium;
oxygen-containing compounds of at least one rare-earth metal
selected from the group consisting of Ce, Pr, Nd, Sm, Eu, Dy, Ho,
Er, and Tm; and oxygen-containing compounds of at least one second
metal selected from the group consisting of Al, Ga, and In; the
amounts of oxygen-containing compounds being selected such that the
final composition of the scintillator is achieved; (2) mixing
together the oxygen-containing compounds to form a mixture; (3)
optionally adding at least one fluxing compound selected from the
group consisting of halides and carbonates of Tb, Al, Ga, In, Y,
La, Gd, Lu, Yb, Ce, Pr, Sm, Eu, Dy, Ho, Er, Tm, Na, K, Rb, and Cs
in the mixture in a quantity sufficient to act as a flux; and (4)
firing the mixture in a reducing atmosphere at a temperature and
for a time sufficient to convert the mixture to a rare
earth-activated terbium-containing garnet scintillator.
[0011] In another aspect of the present invention, a solution of
amounts of oxygen-containing compounds of at least one first metal
selected from the group consisting of terbium and lutetium; at
least one other rare earth metal selected from the group consisting
of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, and Tm; and oxygen-containing
compounds of at least one second metal selected from the group
consisting of Al, Ga, and In is precipitated in a basic solution to
obtain a mixture of hydroxides of the metals. The amounts of
oxygen-containing compounds are selected such that the final
composition of the scintillator is achieved. The mixture of
precipitated hydroxides is calcined in an oxidizing atmosphere. The
calcined material is further thoroughly mixed, and then fired in a
reducing atmosphere at a temperature and for a time sufficient to
convert the calcined mixture to rare earth-activated terbium
containing garnet scintillator.
[0012] In still another aspect of the present invention, an X-ray
detector is provided and comprises a scintillator comprising
terbium-containing garnet activated with at least one rare-earth
metal having a general formula of
(G.sub.1-x-yA.sub.xRE.sub.y).sub.aD.sub.zO.sub.12, wherein G is at
least one metal selected from the group consisting of terbium and
lutetium; A is a member selected from the group consisting of Y,
La, Gd, Lu, and Yb when G is Tb and selected from the group
consisting of Y, La, Gd, Tb, and Yb when G is Lu; RE is at least
one member selected from the group consisting of Ce, Pr, Nd, Sm,
Eu, Dy, Ho, Er, and Tm; D is at least one member selected from the
group consisting of Al, Ga, and In; a is in the range from about
2.8 to and including 3; x is in the range from 0 to about 0.5; y is
in the range from about 0.0005 to about 0.2; and z is in the range
from about 4 to and including 5. In one aspect of the present
invention 4<z<5.
[0013] In still another aspect of the present invention, such an
X-ray detector is incorporated in a CT system.
[0014] Other features and advantages of the present invention will
be apparent from a perusal of the following detailed description of
the invention and the accompanying drawings in which the same
numerals refer to like elements.
BRIEF DESCRIPTION OF DRAWINGS
[0015] FIG. 1 is an emission spectrum of a scintillator of the
present invention having the composition of
(Tb.sub.0.97Ce.sub.0.03)Al.sub.4.9O.s- ub.12 under X-ray excitation
having a peak energy of 60 keV from a tungsten anode.
[0016] FIG. 2 shows an emission spectrum of the same scintillator
under excitation by blue light having a wavelength of 460 nm.
[0017] FIG. 3 shows the decay in emission at wavelength of 570 nm
from the same scintillator after having been excited by
electromagnetic radiation having a wavelength of 460 nm.
DETAILED DESCRIPTION
[0018] The present invention provides rare earth-activated
scintillator having a garnet structure and containing terbium
and/or lutetium. All metals disclosed herein are present in the
scintillator compositions in combined form, usually as the oxide,
rather than in elemental form. In one aspect of the present
invention, the scintillators are responsive to X-ray excitation and
have high light output, reduced afterglow, short decay time, and
high X-ray stopping power.
[0019] As used herein, the term "light output" is the quantity of
visible light emitted by the scintillator after being excited by a
pulse of X-ray having an average intensity of about 33 keV, a peak
intensity of 60 keV, and having a duration of 500 milliseconds. For
ease of comparison, the light output presented in this disclosure
is a relative quantity compared to the light output of an
established standard europium-activated yttrium gadolinium oxide
scintillator. The term "afterglow" is the light intensity emitted
by the scintillator at 100 milliseconds after the X-ray excitation
ceases, reported as a percentage of the light emitted while the
scintillator is excited by the X radiation. The term "decay time,"
"primary decay," or "primary speed" is the time required for the
intensity of the light emitted decreases to about 36.8% (or 1/e) of
the light intensity at the time after the X-ray excitation ceases.
The term "stopping power" refers to the ability of a material to
absorb X-radiation, commonly called the attenuation or absorption.
A material having a high stopping power allows little or no
X-radiation to pass through. The stopping power is directly related
to the density of the scintillator and the elements contained
therein. Thus, it is advantageous to produce scintillators having
high density. The term "radiation damage" refers to the
characteristic of a luminescent material in which the quantity of
light emitted by the luminescent material in response to a given
intensity of stimulating radiation changes after the material has
been exposed to a high radiation dose.
[0020] Higher light output is advantageous because a lower amount
of X-ray excitation energy is required. Thus, the patient is
exposed to a lower dose of X-ray energy. Reduced afterglow is
advantageous because the image is sharper and free from image
artifacts, sometimes referred to as "ghost images." Shorter decay
time is preferred because the scan time can be reduced, resulting
in more efficient use of the CT system. Higher stopping power is
preferred because only a smaller quantity of scintillator is
needed. Thus, thinner detectors are possible, resulting in lower
cost of manufacture. Low radiation damage is advantageous because
the sensitivity of the scintillator to exciting radiation remains
substantially constant over a long-term use.
[0021] The present invention provides a garnet scintillator that is
efficiently excitable by X-radiation and efficiently emits light in
the visible range having a broad spectrum from blue to red (from
about 500 nm to about 770 nm). The scintillator has an emission
peak in the green to yellow range (from about 540 nm to about 600
nm), which includes the range of maximum sensitivity of X-ray image
intensifiers and photodetectors. The scintillator of the present
invention is a rare earth-activated garnet containing terbium
and/or lutetium having a general formula
(G.sub.1-x-yA.sub.xRE.sub.y).sub.aD.sub.zO.sub.12, wherein G is at
least one metal selected from the group consisting of Tb and Lu; A
is a member selected from the group consisting of Y, La, Gd, Lu,
and Yb when G is Tb and selected from the group consisting of Y,
La, Gd, Tb, and Yb when G is Lu; RE is at least one member selected
from the group consisting of Ce, Pr, Nd, Sm, Eu, Dy, Ho, Er, and
Tm; D is at least one member selected from the group consisting of
Al, Ga, and In; a is in the range from about 2.8 to and including
3, preferably from about 2.9 to and including 3; x is in the range
from 0 to about 0.5, preferably from 0 to about 0.3, more
preferably from 0 to about 0.2; and y is in the range from about
0.0005 to about 0.2, preferably from about 0.005 to about 0.1, more
preferably from about 0.005 to about 0.07; and z is in the range
from about 4 to and including 5, preferably from about 4.5 to and
including 5, more preferably from about 4.6 to and including 5.
[0022] In one preferred embodiment, the scintillator is terbium
aluminum garnet activated with cerium having the formula
(Tb.sub.1-yCe.sub.y).sub.- aAl.sub.4.9O.sub.12 where y takes the
values as defined above and a is in the range from about 2.8 to and
including 3.
[0023] In another preferred embodiment of the present invention,
terbium is partially substituted with lutetium, and the
scintillator has the formula of
(Tb.sub.1-x-yLu.sub.xCe.sub.y).sub.aAl.sub.4.9O.sub.12, wherein a,
x, and y take the values as defined above.
[0024] In still another preferred embodiment of the present
invention, the scintillator has the formula of
(Tb.sub.1-xLu.sub.xCe.sub.y)3Al.sub.5O.su- b.12; where
0<x.ltoreq.0.5, and y is defined above.
[0025] In another preferred embodiment, aluminum is partially
substituted with gallium, indium, or a combination thereof. In this
case, the scintillator has the formula of
(Tb.sub.1-yCe.sub.y).sub.3(Al.sub.1-r-sGa-
.sub.rIn.sub.s).sub.zO.sub.12 where y and z are defined above and
0.ltoreq.r.ltoreq.0.5 when 0<s.ltoreq.0.5 and r+s<1, or
0<r.ltoreq.0.5 when 0.ltoreq.s.ltoreq.0.5 and r+s<1.
Preferably, r is in a range from about 0.005 to about 0.3 and more
preferably from about 0.05 to about 0.2; and s is preferably in a
range from about 0.005 to about 0.3 and more preferably from about
0.05 to about 0.2.
[0026] In another preferred embodiment, terbium is partially
substituted by one of Y, Gd, Sm, or a combination thereof and
aluminum is not substituted. In this case, the scintillator has the
formula of
(Tb.sub.1-y-u-v-wCe.sub.yY.sub.uGd.sub.vSm.sub.w).sub.3Al.sub.zO.sub.12
where y and z are defined above, 0.ltoreq.u, v, w.ltoreq.0.5, and
0.0005.ltoreq.y+u+v+w<1. Each of u, v, and w is preferably in a
range from about 0.005 to about 0.3 and more preferably from about
0.005 to about 0.1.
[0027] In still another preferred embodiment, the scintillator has
the formula of (Tb.sub.1-x-yA.sub.xCe.sub.y).sub.3Al.sub.zO.sub.12,
where A is Y or Gd, 0<x.ltoreq.0.5, and y and z are defined
above.
[0028] A scintillator composition of the present invention may be
prepared by a dry or wet synthesis method. A scintillator of the
present invention useful for a detection of high-energy radiation
such as X, .beta., or .gamma. radiation is produced by a dry
synthesis method comprising the steps of: (1) providing amounts of
oxygen-containing compounds of at least one first metal selected
from the group consisting of terbium and lutetium;
oxygen-containing compounds of at least one rare-earth metal
selected from the group consisting of Y, La, Ce, Pr, Nd, Sm, Eu,
Gd, Dy, Ho, Er, Tm, and Yb; and oxygen-containing compounds of at
least one second metal selected from the group consisting of Al,
Ga, and In; the amounts of oxygen-containing compounds being
selected such that the final composition of the scintillator is
achieved; (2) mixing together the oxygen-containing compounds to
form a mixture; and (3) firing the mixture in a reducing atmosphere
at a temperature and for a time sufficient to convert the mixture
to a rare earth-activated terbium-containing garnet
scintillator.
[0029] In another aspect of the present invention, an amount of a
compound selected from the group consisting of halides and
carbonates of at least one metal selected from the group consisting
of Tb, Lu, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Na,
K, Rb, and Cs is added as a fluxing agent into the mixture of the
oxygen-containing compounds before or during the step of mixing. A
quantity of a halide or a carbonate compound of less than about 20,
preferably less than about 10 percent by weight of the total weight
of the mixture is adequate for fluxing purposes. A preferred halide
is fluoride. When an alkali halide or carbonate is used as a
fluxing agent, the scintillator may be preferably washed to remove
residual soluble alkali metal compounds and dried before it is
used.
[0030] The oxygen-containing compounds may be mixed together by any
mechanical method including, but not limited to, stirring or
blending in a high-speed blender or a ribbon blender. The
oxygen-containing compounds may be combined and pulverized together
in a bowl mill, a hammer mill, or a jet mill. The mixing may be
carried out by wet milling especially when the mixture of the
oxygen-containing compounds is to be made into a solution for
subsequent precipitation. If the mixture is wet, it may be dried
first before being fired under a reducing atmosphere at a firing
temperature from about 900.degree. C. to about 1700.degree. C.,
preferably from about 1000.degree. C. to about 1600.degree. C.,
more preferably from about 1200.degree. C. to about 1500.degree. C.
for a time sufficient to convert all of the mixture to the final
garnet composition. The drying may be conducted at atmospheric or
subatmospheric pressure in air or under a flow of a suitable gas
including inert gases and mixtures of air and inert gases at a
temperature sufficient to remove a portion of or substantially all
solvent used in the wet milling process. The firing may be
conducted in a batchwise or continuous process, preferably with a
stirring or mixing action to promote good gas-solid contact. The
firing time depends on the quantity of the mixture to be fired, the
rate of gas conducted through the firing equipment, and the quality
of the gas-solid contact in the firing equipment. Typically, a
firing time up to about 10 hours is adequate. The reducing
atmosphere typically comprises a reducing gas such as hydrogen,
carbon monoxide, or a combination thereof, optionally diluted with
an inert gas, such as nitrogen, helium, neon, argon, krypton,
xenon, or a combination thereof. Alternatively, the crucible
containing the mixture may be packed in a second closed crucible
containing high-purity carbon particles and fired in air so that
the carbon particles react with the limited amount of oxygen
present in the atmosphere inside crucible, thereby, generating
carbon monoxide that is needed to provide the reducing atmosphere.
The fired material may be pulverized afterward to provide a
scintillator in a powder form for further processing into X-ray
detector elements. The powder may be cast with the addition of a
binder into a green element, then further sintered at temperature
in the range of from about 1500.degree. C. to about 1800.degree. C.
to increase the density of the element.
EXAMPLE 1
[0031] The following quantities of oxides of terbium, cerium, and
aluminum and aluminum fluoride were dry blended thoroughly.
[0032] [t5]
[0033] Tb.sub.4O.sub.7:6.805 g
[0034] CeO.sub.2:0.194 g
[0035] Al.sub.2O.sub.3:3.062 g
[0036] AlF.sub.3:0.105 g
[0037] This mixture was placed in a first crucible which is placed
inside a second closed crucible containing particles of a coconut
charcoal were packed with the mixture, and the combined mixture was
fired at 1450.degree. C. for 5 hours in a reducing atmosphere which
is a combination of 10% (by volume) H.sub.2 in nitrogen and gas
generated by the reaction of coconut charcoal in a box furnace. At
the end of 5 hours, the solid was cooled under the same flow of
H.sub.2/N.sub.2 mixture. The final scintillator has the composition
of (Tb.sub.0.97Ce.sub.0.03).sub.3A- l.sub.4.9O.sub.12, as
determined by elemental analysis. Excitation spectrum and emission
spectrum of the scintillator under excitation by X-ray and blue
light having a wavelength of 460 nm were measured and shown in
FIGS. 1 and 2, respectively. The scintillator of the present
invention shows a broad spectrum of emission in the visible range
from about 500 nm to about 770 nm in response to excitation by X
radiation. Thus, the emission covers the range from blue-green to
red light. Therefore, a scintillator of the present invention is
very suitable for detection of X radiation by incorporation in an
X-ray image intensifier or a photodetector.
EXAMPLE 2
[0038] A scintillator composition having the formula of
(Tb.sub.0.72Lu.sub.0.25Ce.sub.0.03).sub.3Al.sub.4.09O.sub.12 was
prepared by the dry synthesis method of Example 1, except that the
following amounts were used:
[0039] [t1]
[0040] Tb.sub.4O.sub.7:4.976 g
[0041] CeO.sub.2:0.191 g
[0042] Lu.sub.2O.sub.3:1.839 g
[0043] Al.sub.2O.sub.3:3.016 g
[0044] AlF.sub.3:0.103 g
EXAMPLE 3
[0045] A scintillator composition having the formula of
(Tb.sub.0.47Lu.sub.0.5Ce.sub.0.03).sub.3Al.sub.4.9O.sub.12 was
prepared by the dry synthesis method of Example 1, except that the
following amounts were used:
[0046] [t2]
[0047] Tb.sub.4O.sub.7:3.201 g
[0048] CeO.sub.2:0.188 g
[0049] Lu.sub.2O.sub.3:3.625 g
[0050] Al.sub.2O.sub.3:2.972 g
[0051] AlF.sub.3:0.102 g
[0052] One or more of the starting materials for the aforementioned
scintillator synthesis may be oxygen-containing compounds other
than oxides, such as nitrates, sulfates, acetates, citrates,
chlorates, or perchlorates. For example, amounts of
Tb.sub.4O.sub.7, Al(NO.sub.3).sub.39H.sub.2O,
Ce(NO.sub.3).sub.36H.sub.2O and AlF.sub.3 are blended and dissolved
in a nitric acid solution. The strength of the acid solution is
chosen to rapidly dissolve the oxygen-containing compounds and the
choice is within the skill of a person skilled in the art. Ammonium
hydroxide is then added in increments to the acidic solution
containing Tb, Ce, and Al while stirring to precipitate a mixture
of hydroxides of Tb, Ce, and Al. An organic base; such as
methanolamine, ethanolamine, propanolamine, dimethanolamine,
diethanolamine, dipropanolamine, trimethanolamine, triethanolamine,
or tripropanolamine; may be used in place of ammonium hydroxide.
The precipitate is filtered, washed with deionized water, and
dried. The dried precipitate is ball milled or otherwise thoroughly
blended and then calcined in air at about 400.degree. C. to about
1600.degree. C. for a sufficient time to ensure a substantially
complete dehydration of the starting material. The calcination may
be carried out at a constant temperature. Alternatively, the
calcination temperature may be ramped from ambient to and held at
the final temperature for the duration of the calcination. The
calcined material is similarly fired at 1200-1600.degree. C. for a
sufficient time under a reducing atmosphere such as H.sub.2, CO, or
a mixture of one of these gases with an inert gas, or an atmosphere
generated by a reaction between a coconut charcoal and the products
of the decomposition of the oxygen-containing compounds to covert
all of the calcined material to the desired scintillator
composition.
[0053] FIG. 3 shows the decay of the emission of visible light at
570 nm wavelength by the scintillator of Example 1 after having
been excited by blue light having a wavelength of 460 nm. It is
evident that the primary speed of this scintillator is less than 50
nanoseconds. In comparison, known commercial scintillators
typically have primary speed in the range of microseconds. Thus,
the emission from scintillators of the present invention decays at
about two to three orders of magnitude faster than some known
commercial scintillators. This comparison can be
semi-quantitatively made with some dopant species in some specific
scintillators, such as cerium dopant in terbium aluminum garnet
scintillator, because the luminescence quantum efficiency of the
Ce.sup.3+ ion is known to be very high (>80%) and thus the
non-radiative processes do not result in a significant increase in
the observe scintillator primary speed. Since the X-ray emission
spectrum shows predominantly the Ce.sup.3+ emission, the decay of
emission upon excitation by visible light can definitively provide
a magnitude for the primary speed of the Ce-activated
scintillators. This is conveniently measured at excitation
wavelength of 460 nm and probed for emission at wavelength of 570
nm.
[0054] Other scintillators of the present invention were also made
with terbium partially substituted by lutetium as disclosed in
Examples 2 and 3 and showed advantageous properties in light
output, afterglow, and speed, as shown in Table 1. The light
output, as shown in Table 1, is a relative quantity compared to an
established standard europium-doped yttrium gadolinium oxide
scintillator (assigned a relative value of 1).
[0055] [t3]
1TABLE 1 Light Afterglow Speed Stopping Power Compostion Output (%)
(microseconds) (1/cm at 70 keV)
(Tb.sub.0.97Ce.sub.0.03)Al.sub.4.9O.sub.12 3 0.04 0.044 30.0
(Tb.sub.0.72Lu.sub.0.25Ce.sub.0.03).sub.3A1.sub.4.9O.sub.12 2 0.02
0.68 33.1
(Tb.sub.0.47Lu.sub.0.5Ce.sub.0.03).sub.3Al.sub.4.9O.sub.12 1.8 0.05
0.09 36.2 (Lu.sub.0.97Ce.sub.0.03)Al.sub.5O.sub.12 1.6 1.84 0.06
42.6
[0056] Table 1 shows that scintillators of the present invention
have much higher light output compared to the standard
europium-doped yttrium gadolinium oxide scintillator and decay time
much shorter than the acceptable level of 500 microseconds. In
addition, when terbium is partially substituted by lutetium, the
afterglow can be drastically reduced.
[0057] The wet process of preparation comprises the steps of (1)
preparing a first solution having appropriate amounts of (a)
compounds of at least one first metal selected from the group
consisting of terbium and lutetium, (b) compounds of at least one
rare-earth element selected from the group consisting of Y, La, Ce,
Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, and Yb, and (c) at least one
compound of at least one second metal selected from the group
consisting of aluminum, gallium, and indium; (2) providing a second
solution selected from the group consisting of ammonium hydroxide,
hydroxides of at least one metal selected from the group consisting
of Tb, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, Lu, Al,
Ga, and In; alkyl esters of a dicarboxylic acid selected from the
group consisting of oxalic acid, malonic acid, succinic acid, and
glutaric acid; and amines selected from the group consisting of
methanolamine, ethanolamine, propanolamine, dimethanolamine,
diethanolamine, dipropanolamine, trimethanolamine, triethanolamine,
and tripropanolamine; and mixture thereof; (3) mixing the first
solution into the second solution to precipitate a mixture of
oxygen-containing compounds of at least one first metal selected
from the group consisting of terbium and lutetium; at least one
rare-earth metal selected from the group consisting of Y, La, Ce,
Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, Tm, Yb, and Lu; and at least one
second metal selected from the group consisting of Al, Ga, and In;
(4) separating the precipitate mixture from the supernatant liquid;
(5) drying the precipitate mixture; (5) optionally calcining in an
oxygen-containing atmosphere; and (6) firing the calcined material
at a temperature for a time sufficient to convert the calcined
material to a rare-earth activated scintillator containing terbium
and/or lutetium. One or more compounds of halides or carbonates of
Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Al, Ga,
In, Na, K, Rb, and Cs may be added in a minor amount into the first
solution, such as up to about 2 mole percent, to act as a fluxing
compound during the firing of the mixture. The first solution may
be added slowly, such as drop-wise, into the second solution while
the second solution is stirred. Calcination may be carried out at a
temperature in the range from about 400.degree. C. to about
900.degree. C. under an atmosphere of oxygen-containing gas, such
as air, oxygen, or a mixture of oxygen and an inert gas selected
from the group consisting of nitrogen, helium, neon, argon,
krypton, and xenon. The firing may be carried out under a condition
as stated above. The calcination and firing atmosphere may be the
same or may have different compositions. The calcination and firing
steps may be conducted in a batch-wise or continuous process with a
static or flowing gas atmosphere. After firing, a scintillator of
the present invention may be further pulverized to produce the
scintillator in the powder form which can be pressed into compacted
scintillators for use in detectors of X-ray CT systems. The powder
may be compacted by a method such as hot pressing or hot isostatic
pressing into desired shaped bodies.
[0058] In another aspect of the present invention, the composition
of the scintillator and the firing temperatures are chosen such
that the final scintillator is substantially a solid solution. A
solid solution is most preferred because the X-ray detecting
element would have a substantially uniform composition, refractive
index, and higher light output.
[0059] Alternatively, a scintillator that has a composition
suitable for single crystal growth may be produced in single
crystal form. In this process, a seed crystal of the desired
composition is introduced into a saturated solution containing
appropriate compounds and new crystalline material is allowed to
grow and add to the seed crystal using any well-known crystal
growth method. For example, single crystals may be grown that have
an approximate composition of (Tb.sub.0.75Lu.sub.0.25).su-
b.3Al.sub.5O.sub.12:Ce.
[0060] While various embodiments are described herein, it will be
appreciated from the specification that various combinations of
elements, variations, equivalents, or improvements therein may be
made by those skilled in the art, and are still within the scope of
the invention as defined in the appended claims.
* * * * *